EP4257552A1 - Verfahren zur herstellung von lithiumhydroxid - Google Patents
Verfahren zur herstellung von lithiumhydroxid Download PDFInfo
- Publication number
- EP4257552A1 EP4257552A1 EP22911002.8A EP22911002A EP4257552A1 EP 4257552 A1 EP4257552 A1 EP 4257552A1 EP 22911002 A EP22911002 A EP 22911002A EP 4257552 A1 EP4257552 A1 EP 4257552A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lithium
- lithium hydroxide
- containing solution
- carbonate
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 title claims abstract description 354
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 71
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 71
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 59
- 239000012535 impurity Substances 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 30
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 claims abstract description 24
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000004090 dissolution Methods 0.000 claims abstract description 20
- 238000000909 electrodialysis Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 15
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 10
- 238000007664 blowing Methods 0.000 claims abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000010979 pH adjustment Methods 0.000 claims description 55
- 239000007788 liquid Substances 0.000 claims description 41
- 238000005342 ion exchange Methods 0.000 claims description 33
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 19
- 239000003513 alkali Substances 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003456 ion exchange resin Substances 0.000 claims description 13
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 13
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 23
- 239000002184 metal Substances 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 16
- 150000002739 metals Chemical class 0.000 abstract description 13
- 239000000243 solution Substances 0.000 description 92
- 239000011734 sodium Substances 0.000 description 16
- 229910052708 sodium Inorganic materials 0.000 description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 239000012528 membrane Substances 0.000 description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 10
- 239000011572 manganese Substances 0.000 description 10
- 229910052748 manganese Inorganic materials 0.000 description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000012267 brine Substances 0.000 description 5
- -1 calcium Chemical class 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 229920001429 chelating resin Polymers 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 240000001973 Ficus microcarpa Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Definitions
- the present invention relates to a method for producing lithium hydroxide. More specifically, the present invention relates to a method for producing lithium hydroxide including a conversion step by electrodialysis.
- lithium hydroxide is obtained by, for example, adding slaked lime to lithium carbonate to substitute a hydroxyl group.
- lithium carbonate is used as a starting material as a starting material because it is less likely to degenerate compared with other lithium compounds, and can be stored for a long time.
- this producing method for obtaining the lithium hydroxide from the lithium carbonate has a problem of an increased production cost due to a high cost of agents.
- Patent Document 1 discloses a method that uses electrodialysis (membrane separation) and ion-exchange resin as a method for producing lithium hydroxide from lithium carbonate. This method discloses that polyvalent metals with a valence of two or more, such as calcium described above, can be reduced.
- Patent Document 1 JP-A-2009-270189
- Non-Patent Document 1 Masao Kobayashi, Lithium, its History, Source, Production, and Application, Journal of the Mining Institute of Japan, Japan, 1984, volume 100 issue 1152, 115-122
- concentrations of the polyvalent metals with a valence of two or more, such as calcium, in an electrolyte are increased in the electrodialysis, a used barrier membrane is easily damaged.
- concentrations of the polyvalent metals, such as calcium, in the electrolyte need to be less than 0.05 mg/L before the electrodialysis is performed in order to reduce this damage.
- a method for producing lithium hydroxide according to a first invention includes steps (1) to (5) below: (1) a hydrocarbonating step of blowing carbon dioxide to a slurry of a mixture of water and rough lithium carbonate to obtain a lithium hydrogen carbonate solution; (2) a decarbonation step of heating the lithium hydrogen carbonate solution to obtain a purified lithium carbonate; (3) an acid solution dissolution step of dissolving the purified lithium carbonate in an acid solution to obtain a first lithium containing solution; (4) an impurity removal step of removing a part of metal ions from the first lithium containing solution to obtain a second lithium containing solution; and (5) a conversion step of converting lithium salt contained in the second lithium containing solution into lithium hydroxide by electrodialysis to obtain a lithium hydroxide containing solution in which the lithium hydroxide is dissolved.
- the method for producing lithium hydroxide according to a second invention which is in the first invention, includes a crystallization step of solidifying the lithium hydroxide dissolved in the lithium hydroxide containing solution after the conversion step.
- the impurity removal step includes: a pH adjustment step of adjusting a pH by adding alkali to the first lithium containing solution to obtain a post-pH adjustment liquid; and an ion exchange step of bringing the post-pH adjustment liquid into contact with ion-exchange resin to obtain the second lithium containing solution.
- the impurity removal step includes: a step of adding an oxidant to the first lithium containing solution to obtain a post-oxidation liquid; a pH adjustment step of adjusting a pH by adding alkali into the post-oxidation liquid to obtain a post-pH adjustment liquid; and an ion exchange step of bringing the post-pH adjustment liquid into contact with ion-exchange resin to obtain the second lithium containing solution.
- the pH of the post-pH adjustment liquid after the pH adjustment step is 6 or more and 10 or less.
- the alkali includes lithium carbonate or lithium hydroxide.
- the lithium carbonate is the purified lithium carbonate obtained in the decarbonation step.
- the lithium hydrogen carbonate solution is heated at 60°C or more and 90°C or less.
- executing the hydrocarbonating step, the decarbonation step, and the acid solution dissolution step in the step before the conversion step by electrodialysis allows reliably removing the metals other than lithium, and therefore, a purity of the obtained lithium hydroxide can be increased. Additionally, the concentrations of polyvalent metals with a valence of two or more, such as calcium, in the electrolyte can be lowered, and therefore, a damage of a barrier membrane used in the conversion step after these steps can be reduced.
- the crystallization step of solidifying the lithium hydroxide is provided after the conversion step, and therefore, the lithium hydroxide can be solidified to have a high purity using a difference in solubility.
- the impurity removal step includes the ion exchange step of using the ion-exchange resin and the pH adjustment step of adding the alkali before the ion exchange step, and therefore, the pH can be adjusted to be appropriate for the subsequent ion exchange step in the pH adjustment step and a removal rate of divalent or more metals is substantially improved in the ion exchange step.
- the impurity removal step includes the ion exchange step of using the ion-exchange resin, and the oxidation step of adding the oxidant and the pH adjustment step of adding the alkali before the ion exchange step, and therefore, manganese can be removed when the manganese is contained in the first lithium containing solution, and the pH can be adjusted to be appropriate for the subsequent ion exchange step in the pH adjustment step, thereby substantially improving a removal rate of divalent or more metals in the ion exchange step.
- the pH of the post-pH adjustment liquid after the pH adjustment step is 6 or more and 10 or less, and therefore, the impurities are removed with more certainty in the ion exchange step after the pH adjustment step.
- the alkali contains the lithium carbonate or lithium hydroxide, and therefore, the added alkali can be avoided from being added with impurities, such as sodium or potassium.
- the lithium carbonate is the purified lithium carbonate obtained in the decarbonation step, and therefore, the use of the product obtained in the previous step allows saving an extra cost.
- the heating is 60°C or more and 90°C or less, and therefore, a process period in the decarbonation step can be shortened.
- the method for producing lithium hydroxide according to the present invention includes the steps (1) to (5) below; (1) a hydrocarbonating step: a step of blowing carbon dioxide to a slurry of a mixture of water and rough lithium carbonate to obtain a lithium hydrogen carbonate solution; (2) a decarbonation step: a step of heating the lithium hydrogen carbonate solution to obtain purified lithium carbonate; (3) an acid solution dissolution step: a step of dissolving the purified lithium carbonate in an acid solution to obtain a first lithium containing solution; (4) an impurity removal step: a step of removing a part of metal ions from the first lithium containing solution to obtain a second lithium containing solution; (5) a conversion step: a step of converting lithium salt contained in the second lithium containing solution into lithium hydroxide by electrodialysis to obtain a lithium hydroxide containing solution in which the lithium hydroxide is dissolved.
- the present invention allows reliably removing metals other than lithium by executing the hydrocarbonating step, the decarbonation step, and the acid solution dissolution step in a step before the conversion step by electrodialysis, thereby allowing an increased purity of obtained lithium hydroxide. Additionally, concentrations of polyvalent metals with a valence of two or more, such as calcium, in an electrolyte can be lowered, thereby allowing a reduced damage of a barrier membrane used in the conversion step after these steps.
- the method for producing lithium hydroxide it is preferred to provide a crystallization step of solidifying the lithium hydroxide dissolved in the lithium hydroxide containing solution after the conversion step.
- This aspect allows solidifying the lithium hydroxide to have a high purity using a difference in solubility.
- the impurity removal step includes a pH adjustment step of adjusting a pH by adding alkali into the first lithium containing solution to obtain a post-pH adjustment liquid and an ion exchange step of bringing the post-pH adjustment liquid into contact with ion-exchange resin to obtain the second lithium containing solution.
- This aspect allows the pH to be adjusted to be appropriate for the subsequent ion exchange step, and a removal rate of divalent or more metals is substantially improved in the ion exchange step.
- the impurity removal step includes a step of adding an oxidant to the first lithium containing solution to obtain a post-oxidation liquid, a pH adjustment step of adjusting a pH by adding alkali into the post-oxidation liquid to obtain a post-pH adjustment liquid, and an ion exchange step of bringing the post-pH adjustment liquid into contact with ion-exchange resin to obtain the second lithium containing solution.
- This aspect allows removing manganese when the manganese is contained in the first lithium containing solution, and allows pH to be adjusted to be appropriate for the subsequent ion exchange step in the pH adjustment step, and a removal rate of divalent or more metals is substantially improved in the ion exchange step.
- a pH of the post-pH adjustment liquid after the pH adjustment step is preferred to be 6 or more and 10 or less. This aspect allows removing impurities with more certainty in the ion exchange step after the pH adjustment step.
- the alkali used in the pH adjustment step is preferred to be the purified lithium carbonate obtained in the decarbonation step. This aspect allows avoiding impurities, such as sodium or potassium, from being added. Additionally, since the product obtained from the previous step is used, an extra cost can be saved.
- the lithium hydrogen carbonate solution in the decarbonation step, is heated at 60°C or more and 90°C or less. This aspect allows shortening a process period in the decarbonation step.
- Fig. 1 illustrates a flowchart of a method for producing lithium hydroxide according to a first embodiment of the present invention.
- This embodiment executes (1) a hydrocarbonating step, (2) a decarbonation step, (3) an acid solution dissolution step, (4) an impurity removal step, and (5) conversion step in this order.
- the hydrocarbonating step is performed first.
- the hydrocarbonating step is a step of blowing carbon dioxide to a slurry of a mixture of water and rough lithium carbonate to obtain a lithium hydrogen carbonate solution.
- the "rough lithium carbonate” means one that contains lithium carbonate as a main component and has a high proportion of impurities compared with a "purified lithium carbonate" described later.
- lithium carbonate high in impurity obtained by the method disclosed in Masao Kobayashi, Lithium, its History, Source, Production, and Application, Journal of the Mining Institute of Japan, Japan, 1984, volume 100 issue 1152, 115-122 from a brine, such as a salt lake brine, a geothermal brine, and a petroleum brine, or a leaching solution of lithium ore or the like corresponds to the "rough lithium carbonate.”
- the rough lithium carbonate reacts with carbon dioxide and water to be converted into lithium hydrogen carbonate high in solubility, and thus, a lithium hydrogen carbonate solution is obtained. That is, the lithium hydrogen carbonate melts into a liquid to turn into the lithium hydrogen carbonate solution, and other sparingly soluble impurities solidifies. For example, this impurity is calcium carbonate. Thus separating solid and liquid allows removing the calcium carbonate and the like as the impurities.
- the temperature is preferred to be 20°C or more and 40°C or less.
- the blown carbon dioxide preferably has an amount immediately before the unreacted and insoluble carbon dioxide starts to come out in a form of air bubbles.
- the lithium hydrogen carbonate in the decarbonation step, by heating the lithium hydrogen carbonate solution, the lithium hydrogen carbonate is converted into the purified lithium carbonate having a low solubility, and the purified lithium carbonate is precipitated again to obtain the purified lithium carbonate.
- the rough lithium carbonate contains a high concentration of sodium in some cases.
- the lithium carbonate in the rough lithium carbonate is dissolved as the lithium hydrogen carbonate having a high solubility in the hydrocarbonating step.
- the lithium hydrogen carbonate is turned into lithium carbonate again in a form of the purified lithium carbonate in the decarbonation step to precipitate the purified lithium carbonate.
- the "purified lithium carbonate” means one that contains lithium carbonate as a main component and has a low proportion of impurities compared with the "rough lithium carbonate” described above.
- the sodium is almost removed from the precipitated purified lithium carbonate, and thus, the purity of the purified lithium carbonate can be increased.
- the purified lithium carbonate as the precipitate and the supernatant are separated into solid and liquid, thus allowing obtaining the purified lithium carbonate as a solid material.
- the decarbonation step according to the embodiment was performed at 80°C, but it is not limited to this. For example, it is preferred to be performed at 60°C or more and 90°C or less. This aspect allows shortening a process period in the decarbonation step.
- the heating method is not particularly limited, and it is preferred to employ a method that corresponds to a scale of a reaction container. For example, a Teflon (Registered Trademark) heater or steam heating can be employed.
- a filter press is used in the solid-liquid separation in the decarbonation step according to the embodiment.
- the purified lithium carbonate obtained in the decarbonation step is dissolved with an acid solution to obtain a lithium salt solution.
- the use of the lithium carbonate for the subsequent conversion step causes two problems: the low solubility of the lithium carbonate allows only conversion with thin liquid, and efficiency is poor (the size of facility becomes large with respect to throughput); and carbonic acid gas is possibility generated during conversion, possibly damaging the membrane.
- the purified lithium carbonate is dissolved with an acid solution to turn into a first lithium salt solution as the lithium salt solution. Since the pH decreases after the acid solution dissolution, adjusting the pH to the pH appropriate for impurity removal is preferred in the ion exchange step.
- the acid used in the acid solution dissolution step is hydrochloric acid, sulfuric acid, nitric acid, and the like.
- Hydrochloric acid is used in this embodiment, and a lithium chloride solution is obtained as a lithium salt solution in the acid solution dissolution step.
- the chemical reaction formula is illustrated in Formula 3. [Formula 3] Li 2 CO 3 + 2HCl ⁇ 2LiCl + H 2 O + CO 2
- the amount of acid solution used in the acid solution dissolution step is preferably the minimum necessary amount.
- the pH is preferably adjusted to be 8.5.
- Fig. 1 illustrates a flowchart illustrating a configuration of the impurity removal step according to the embodiment.
- the impurity removal step includes the pH adjustment step and the ion exchange step. Note that the impurity removal step is not limited to the configuration illustrated here.
- the pH adjustment step alkali is added to the first lithium containing solution and a pH is adjusted to obtain a pH adjusted liquid. At this time, depending on the adjustment pH or the impurity concentration, a pH adjustment sediment containing some impurities is obtained.
- the post-pH adjustment liquid is adjusted to a pH appropriate for removing impurities, such as Ca and Mg, in the ion exchange step subsequent to this.
- the pH is preferred to be 6 or more and 10 or less. When the pH is smaller than 6, the impurity removal in the ion exchange step may be insufficient. When the pH is larger than 10, an amount of added alkali is too much.
- the post-pH adjustment liquid is even more preferred to be pH 7.5 or more and pH 8.5 or less. This is because an additive amount of the neutralizer can be reduced and a necessary impurity removal performance can be expected.
- the alkali is preferred to be one that does not contain sodium or potassium.
- the alkali is preferred to contain lithium carbonate or lithium hydroxide.
- the lithium carbonate needs to be lithium carbonate with a 99% or more purity
- the lithium hydroxide needs to be lithium hydroxide with a 99% or more purity.
- this lithium carbonate is more preferred to be the purified lithium carbonate obtained after undergoing the above-described decarbonation step. This aspect allows avoiding the impurities, such as sodium or potassium, from being added. Additionally, the use of the product obtained in the previous step allows saving an extra cost.
- a second lithium containing solution from which a part of impurities has been removed is obtained. While in the ion exchange step, divalent or more metal ions are removed, calcium, aluminum, manganese, and magnesium by an amount of the solubility that remains corresponding to the pH in the pH adjustment step are also removed at this time.
- Chelating resin is preferably used as the ion-exchange resin.
- iminodiacetic acid resin can be used.
- Amberlite IRC748 can be used.
- a preferred value is determined as the pH of the post-pH adjustment liquid in the ion exchange step depending on the ion-exchange resin.
- the ion exchange step is preferably performed directly on the first lithium containing solution obtained in the acid solution dissolution step.
- the method for contacting the ion-exchange resin and the post-pH adjustment liquid is preferably a column method. However, there may be a case where a batch mixing method is employed.
- lithium salt contained in the second lithium containing solution is converted into lithium hydroxide to obtain a lithium hydroxide containing solution in which lithium hydroxide is dissolved.
- the lithium salt is lithium chloride.
- the lithium salt is dissolved with the acid used in the acid solution dissolution step in the impurity removal step.
- an electrodialysis using a bipolar membrane is performed to convert these aqueous solutions into the lithium hydroxide containing solution containing lithium hydroxide and hydrochloric acid.
- lithium chloride in the second lithium containing solution is decomposed, lithium ions of lithium chloride pass through a cation membrane and bind to hydroxide ions to become lithium hydroxide, and chloride ions pass through an anion membrane to become hydrochloric acid.
- the recovered hydrochloric acid can be recycled to the elution step. Accordingly, the usage of mineral acid can be reduced.
- an electrodialysis using an ion-exchange membrane corresponds to the conversion step in addition to the electrodialysis using the bipolar membrane.
- a cation-exchange membrane is used as the ion-exchange membrane, lithium hydroxide is generated in a cathode chamber.
- Fig. 3 depicts a flowchart of the impurity removal step of the method for producing lithium hydroxide according to the second embodiment of the present invention.
- This embodiment differs from the first embodiment in that the oxidation step is included before the pH adjustment step in the impurity removal step and is otherwise same as the first embodiment.
- the following describes the neutralization step according to the second embodiment.
- the oxidation step is a step of adding an oxidant, such as air, oxygen, and sodium hypochlorite, to the first lithium containing solution obtained in the acid solution dissolution step to oxidize manganese in the first lithium containing solution and obtain insoluble manganese dioxide, thereby precipitating to remove the manganese dissolved in the liquid to obtain a post-oxidation liquid.
- an oxidant such as air, oxygen, and sodium hypochlorite
- the oxidant used in the oxidation step air, oxygen, sodium hypochlorite, or the like can be employed.
- the first lithium containing solution has a redox potential set to a pH and an electric potential in a region of manganese dioxide in a Pourbaix diagram.
- the obtained post-oxidation liquid is put to the pH adjustment step after the oxidation step.
- a crystallization step of solidifying lithium hydroxide dissolved in the lithium hydroxide containing solution is provided after the conversion step.
- the crystallization step is indicated by the dotted line in Fig. 1 .
- lithium hydroxide containing solution obtained in the conversion step When the lithium hydroxide containing solution obtained in the conversion step is evaporated to dryness, lithium hydroxide is obtained.
- this lithium hydroxide containing solution contains alkali metals, such as sodium or potassium, and the direct evaporation to dryness causes a solid material obtained from it to contain much hydroxides other than lithium hydroxide.
- the crystallization step of solidifying lithium hydroxide dissolved in the lithium hydroxide containing solution is preferably provided after the conversion step.
- the crystallization step by solidifying the lithium hydroxide dissolved in the lithium hydroxide containing solution, a solid lithium hydroxide is obtained.
- a crystallization mother liquor is obtained together with the solid lithium hydroxide.
- lithium becomes a lithium hydroxide
- chlorine ions as anions also pass through the membrane to be contained in the lithium hydroxide containing solution.
- the difference in solubility between the respective hydroxides is used to solidify the lithium hydroxide and separate contained impurities.
- the lithium hydroxide containing solution is heated to be concentrated.
- the concentration of metal ions contained in the liquid increases, and lithium hydroxide having a relatively low solubility is deposited and solidified first.
- the deposited lithium hydroxide is recovered as the solid lithium hydroxide.
- sodium hydroxide or potassium hydroxide having relatively high solubility is not deposited and remains in the aqueous solution. Therefore, the purity of the recovered lithium hydroxide increases.
- the solubility of lithium hydroxide is 13.2 g/100 g-water, and it is seen that the solubility of lithium hydroxide is significantly low compared with 174 g/100 g-water of sodium hydroxide and 154 g/100 g-water of potassium hydroxide. Since the chlorine ion is 2 g/L also during the operation of heating to concentrate, the chlorine ion is not deposited as chloride of the alkali metal in the lithium hydroxide.
- This step can be industrially performed with a continuous crystallization using a crystallization can. It can be performed also with a batch crystallization.
- the crystallization mother liquor generated in the crystallization step is a concentrated alkaline aqueous solution. Since the crystallization mother liquor contains lithium hydroxide by an amount of the solubility, repeating the lithium adsorption step increases a lithium recovery rate. In addition, the neutralizer cost decreases.
- the purified lithium carbonate obtained in the above-described decarbonation step was added to the first lithium containing solution obtained in the acid solution dissolution step, and a pH was adjusted to remove impurities in the ion exchange step.
- the stirring and mixing was performed to obtain pH of 8.4, and a post-pH adjustment liquid was obtained. This step was all performed at ordinary temperature. Contained metals as the impurities are shown in Table 4. It is seen that the content of sodium is significantly reduced by undergoing the decarbonation step, the acid solution dissolution step, and the pH adjustment step.
- Fig. 4 illustrates a relation between an energizing time and a lithium concentration in the lithium hydroxide containing solution.
- the lithium concentration in the lithium hydroxide containing solution increased along with the energization, and was concentrated to 28 g/L to 29 g/L in the end.
- Table 6 shows a metal concentration after the electrodialysis.
- Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the decarbonation step was not performed in the steps of Example 1. Other than this, Comparative Example 1 was all performed under the same conditions. That is, the lithium hydrogen carbonate solution obtained in the hydrocarbonating step was directly added with hydrochloric acid to perform the acid solution dissolution step, and thereafter, a lithium hydroxide containing solution was obtained through the impurity removal step and the conversion step. The result is shown in Table 8. Compared with Table 6, it is seen that a significantly high concentration of sodium is contained.
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